1. Field of the Invention
The invention relates to activating a hydrocarbon synthesis catalyst with hydrogen and ammonia. More particularly, the invention relates to forming an active hydrocarbon synthesis catalyst, including a Fischer-Tropsch type of hydrocarbon synthesis catalyst, by contacting a hydrocarbon synthesis catalyst precursor, comprising at least one catalytic metal component, with a reducing gas comprising a mixture of hydrogen and ammonia, at conditions effective to reduce the precursor and form an activated catalyst, and to a hydrocarbon synthesis process using the catalyst.
2. Background of the Disclosure
The synthesis of hydrocarbons, including oxygenated hydrocarbons such as methanol, from a synthesis gas comprising a mixture of H2 and CO is well known. The synthesis gas feed is contacted with a Fischer-Tropsch catalyst at conditions effective for the H2 and CO in the feed gas to react and form hydrocarbons. The synthesis is known as a Fischer-Tropsch hydrocarbon synthesis. Depending on the catalyst and conditions, the hydrocarbons may range from oxygenated compounds such as methanol and higher molecular weight alcohols, to high molecular weight paraffins which are waxy solids at room temperature. The process also makes, in lesser amounts, alkenes, aromatics, organic acids, ketones, aldehydes and esters. The synthesis is conducted in a fixed or fluidized catalyst bed reactor or in a liquid phase slurry reactor. Hydrocarbon synthesis catalysts are also well known and typically include a composite of at least one iron group catalytic metal component supported on, or composited with, with at least one inorganic refractory metal oxide support material, such as alumina, amorphous, silica-alumina, zeolites and the like. Various catalyst preparation methods have been used to form hydrocarbon synthesis catalysts, including impregnation, incipient wetness, compositing, ion exchange and other known techniques, to form a catalyst precursor. The precursor must be activated to form the catalyst. Typical activation methods include oxidation or calcination, followed by reduction in flowing hydrogen, multiple oxidation-reduction cycles and also reduction without prior oxidation. Examples of catalyst preparation and activation methods for Fischer-Tropsch hydrocarbon synthesis catalysts are disclosed in, for example, U.S. Pat. Nos. 4,086,262, 4,492,774 and 5,545,674.
The invention relates to forming an active hydrocarbon synthesis catalyst, including a Fischer-Tropsch type of hydrocarbon synthesis catalyst, by contacting a hydrocarbon synthesis catalyst precursor, comprising at least one catalytic metal component, with a reducing gas comprising a mixture of hydrogen and ammonia, at conditions of temperature and pressure effective to reduce the precursor and form an active catalyst, and to a hydrocarbon synthesis process using the activated catalyst. It has been found that forming the hydrocarbon synthesis catalyst by reducing the precursor, with a reducing gas comprising a mixture of hydrogen and ammonia, improves the properties of the resulting activated catalyst with respect to at least one of increased C5+ selectivity, increased alpha (Schultz-Flory alpha) of the synthesis reaction and a reduction in methane make. These benefits are unexpected, in view of the fact that ammonia is a well known hydrocarbon synthesis catalyst poison. The catalyst precursor preferably comprises at least one catalytic metal component and at least one metal oxide catalyst support component.
The catalyst precursor may or may not be calcined prior to the reduction in the mixture of hydrogen and ammonia. The mixture of hydrogen and ammonia reducing gas may be substantialy comprised of hydrogen and ammonia or it may contain one or more diluent gasses which do not adversely effect or interfere with the activation, such as methane or argon and the like. The amount of ammonia present in the reducing gas will broadly range from 0.01 to 15 mole %, preferably 0.01 to 10 mole %, more preferably from 0.1 to 10 mole % and still more preferably from 0.5 to 7 mole %, based on the total gas composition. The hydrogen to ammonia mole ratio in the gas will range from 1000:1 to 5:1 and preferably from 200:1 to 10:1.
Thus, in one embodiment the invention is a process which comprises contacting a Fischer-Tropsch type of hydrocarbon synthesis catalyst precursor, comprising at least one catalytic metal component, and preferably at least one catalytic metal component and a metal oxide support type of component, with a reducing gas comprising a mixture of hydrogen and ammonia, at conditions effective to reduce the precursor and form an active catalyst. In another embodiment, the invention comprises a process for synthesizing hydrocarbons from a synthesis gas which comprises a mixture of H2 and CO, wherein the synthesis gas contacts with a Fischer-Tropsch type of hydrocarbon synthesis catalyst, at reaction conditions effective for the H2 and CO in the gas to react and form hydrocarbons and wherein the catalyst comprises a composite of at least one catalytic metal component and preferably also a metal oxide support component, and has been formed by contacting a catalyst precursor with a reducing gas comprising a mixture of hydrogen and ammonia, at conditions effective to reduce the precursor and form the catalyst. In a still further embodiment, at least a portion of the synthesized hydrocarbons are liquid at the synthesis reaction conditions. The conditions of temperature and pressure required to reduce the precursor and form a catalyst with a reducing gas comprising a mixture of hydrogen and ammonia in the practice of the invention, are the same conditions used for conventional hydrocarbon synthesis catalyst reduction and activation with hydrogen, in the absence of ammonia.
Hydrocarbon synthesis catalysts are well known and a typical Fischer-Tropsch hydrocarbon synthesis catalyst will comprise, for example, catalytically effective amounts of one or more Group VIII metal catalytic components such as Fe, Ni, Co and Ru. Preferably the catalyst comprises a supported catalyst, wherein the one or more support components of the catalyst will comprise an inorganic refractory metal oxide. The metal oxide support component is preferably one which is difficult to reduce, such an oxide of one or more metals of Groups III, IV, V, VI, and VII. The metal Groups referred to herein are those found in the Sargent-Welch Periodic Table of the Elements,(copyright) 1968. Typical support components include one or more of alumina, silica, and amorphous and crystalline aluminosilicates, such as zeolites. Particularly preferred support components are the Group IVB metal oxides, especially those having a surface area of 100 m2/g or less and even 70 m2/g or less. These support components may, in turn, be supported on one or more support materials. Titania, and particularly rutile titania, is a preferred support component, especially when the catalyst contains a cobalt catalytic component. Titania is a useful component, particularly when employing a slurry hydrocarbon synthesis process, in which higher molecular weight, primarily paraffinic liquid hydrocarbon products are desired. In some cases in which the catalyst comprises catalytically effective amounts of Co, it will also comprise one or more components or compounds of Re, Ru, Fe, Ni, Th, Zr, Hf, U, Mg and La, some of which are effective as promoters. A combination of Co and Ru is often preferred. Useful catalysts and their preparation are known and illustrative, but nonlimiting examples may be found, for example, in U.S. Pat. Nos. 4,568,663; 4,663,305; 4,542,122; 4,621,072 and 5,545,674.
The catalyst precursor is prepared by any convenient and known method, such as impregnation, incipient wetness, ion exchange, kneading, precipitation or coprecipitation, melt deposition or any other known compositing techniques. The catalytic metal component is typically applied as a solution of a compound of the metal that decomposes during the subsequent reduction or calcination, followed by reduction with the hydrogen and ammonia mixture according to the practice of the invention. For example, a cobalt component is typically applied to a support component as a nitrate salt. It is not uncommon to calcine the precursor after each application of reducible catalytic metal compound. After forming and extruding the precursor composite, it is typically pilled and dried. The precursor is then reduced or calcined and reduced, to form the catalyst. In the prior art, the reduction is achieved by contacting the precursor with flowing hydrogen or a hydrogen reducing gas, at conditions effective to reduce the catalytically active metal component (e.g., cobalt) to the metal form. A common method is known as the R-O-R method, in which the precursor is reduced in hydrogen, then calcined, followed by reducing again. In the prior art methods, the reducing hydrogen gas can be neat (all hydrogen), or mixed with one or more diluent gasses (e.g., methane, argon) which are inert towards the reduction. In the practice of the invention, the R-O-R method may also be used and a conventional hydrogen reducing gas employed for the first reduction, prior to calcination. However, in the practice of the invention, the second and final reduction, which is applied after the calcination, is achieved using a reducing gas comprising a mixture of hydrogen and ammonia. Typical reducing conditions effective for forming the catalyst comprising the reduced metal component on the support from the precursor, range from xc2xd to 24 hours, 200-500xc2x0 C., 1-100 bar, and a GHSV of 50-10000. The actual conditions will depend on the hydrogen concentration in the reducing gas, as well as the metal to be reduced and its precursor form (e.g., salt or oxide). In the catalyst forming and activation process of the invention, the catalyst precursor which may or may not have been calcined, is contacted with a reducing gas comprising a mixture of hydrogen and ammonia, at typical reducing conditions, as set forth above, similar to those used for normal reduction. The precursor may be merely the dried composite without calcining, a calcined composite, or a composite in which multiple catalytic metal salt depositions have been made onto the support, with or without calcining after each deposition. In the case of the R-O-R procedure, the catalyst of the invention is formed if during the second, or final reduction, the reducing gas comprises the hydrogen and ammonia mixture. Catalyst activation may be conducted according to the process of the invention, either prior to loading it into the hydrocarbon synthesis reactor or in-situ in the hydrocarbon synthesis reactor.
The catalyst formed according to the process of the invention may be used in either a fixed bed, fluid bed or slurry hydrocarbon synthesis processes, for forming hydrocarbons from a synthesis gas comprising a mixture of H2 and CO. These processes are well known and documented in the literature. In all of these processes, the synthesis gas is contacted with a suitable Fischer-Tropsch type of hydrocarbon synthesis catalyst, at reaction conditions effective for the H2 and CO in the gas to react and form hydrocarbons. Depending on the process, the catalyst and synthesis reaction variables, some of these hydrocarbons will be liquid, some solid (e.g., wax) and some gas at standard room temperature conditions of temperature and pressure of 25xc2x0 C. and one atmosphere, particularly if a catalyst having a catalytic cobalt component is used. In a fluidized bed hydrocarbon synthesis process, all of the products are vapor or gas at the reaction conditions. In fixed bed and slurry processes, the reaction products will comprise hydrocarbons which are both liquid and vapor at the reaction conditions. Slurry hydrocarbon synthesis processes are sometimes preferred, because of their superior heat (and mass) transfer characteristics for the strongly exothermic synthesis reaction and because they are able to produce relatively high molecular weight, paraffinic hydrocarbons when using a cobalt catalyst. In a slurry hydrocarbon synthesis process, a synthesis gas comprising a mixture of H2 and CO is bubbled up as a third phase through a slurry in a reactor which comprises a particulate Fischer-Tropsch type hydrocarbon synthesis catalyst dispersed and suspended in a slurry liquid comprising hydrocarbon products of the synthesis reaction which are liquid at the reaction conditions. The mole ratio of the hydrogen to the carbon monoxide in the synthesis gas may broadly range from about 0.5 to 4, but is more typically within the range of from about 0.7 to 2.75 and preferably from about 0.7 to 2.5. The stoichiometric mole ratio for a Fischer-Tropsch hydrocarbon synthesis reaction is 2.0, but it can be increased to obtain the amount of hydrogen desired from the synthesis gas for other than the hydrocarbon synthesis reaction. In a slurry hydrocarbon synthesis process, the mole ratio of the H2 to CO is typically about 2.1/1. Reaction conditions effective for the various hydrocarbon synthesis processes will vary somewhat, depending on the type of process, catalyst composition and desired products. Typical conditions effective to form hydrocarbons comprising mostly C5+ paraffins, (e.g., C5+-C200) and preferably C10+ paraffins, in a slurry process employing a catalyst comprising a supported cobalt component include, for example, temperatures, pressures and hourly gas space velocities in the range of from about 320-600xc2x0 F., 80-600 psi and 100-40,000 V/hr/V, expressed as standard volumes of the gaseous CO and H2 mixture (0xc2x0 C., 1 atm) per hour per volume of catalyst, respectively. These conditions nominally apply to the other processes as well.
Hydrocarbons produced by a hydrocarbon synthesis process according to the practice of the invention are typically upgraded to more valuable products, by subjecting all or a portion of the C5+ hydrocarbons to fractionation and/or conversion. By conversion is meant one or more operations in which the molecular structure of at least a portion of the hydrocarbon is changed and includes both noncatalytic processing (e.g., steam cracking), and catalytic processing (e.g., catalytic cracking) in which a fraction is contacted with a suitable catalyst. If hydrogen is present as a reactant, such process steps are typically referred to as hydroconversion and include, for example, hydroisomerization, hydrocracking, hydrodewaxing, hydrorefining and the more severe hydrorefining referred to as hydrotreating, all conducted at conditions well known in the literature for hydroconversion of hydrocarbon feeds, including hydrocarbon feeds rich in paraffins. Illustrative, but nonlimiting examples of more valuable products formed by conversion include one or more of a synthetic crude oil, liquid fuel, olefins, solvents, lubricating, industrial or medicinal oil, waxy hydrocarbons, nitrogen and oxygen containing compounds, and the like. Liquid fuel includes one or more of motor gasoline, diesel fuel, jet fuel, and kerosene, while lubricating oil includes, for example, automotive, jet, turbine and metal working oils. Industrial oil includes well drilling fluids, agricultural oils, heat transfer fluids and the like.